Innately designed to induce physiological changes,pharmaceuticals are foreknowingly hazardous to the ecosystem.Advanced oxidation processes(AOPs)are recognized as a set of contemporary and highly efficient methods bei...Innately designed to induce physiological changes,pharmaceuticals are foreknowingly hazardous to the ecosystem.Advanced oxidation processes(AOPs)are recognized as a set of contemporary and highly efficient methods being used as a contrivance for the removal of pharmaceutical residues.Since reactive oxygen species(ROS)are formed in these processes to interact and contribute directly toward the oxidation of target contaminant(s),a profound insight regarding the mechanisms of ROS leading to the degradation of pharmaceuticals is fundamentally significant.The conceptualization of some specific reaction mechanisms allows the design of an effective and safe degradation process that can empirically reduce the environmental impact of themicropollutants.This review mainly deliberates themechanistic reaction pathways for ROS-mediated degradation of pharmaceuticals often leading to complete mineralization,with a focus on acetaminophen as a drug waste model.展开更多
Understanding the charge/discharge mechanism of batteries plays an important role in the development of high-performance systems,but extremely complicated reactions are involved.Because these complex phenomena are als...Understanding the charge/discharge mechanism of batteries plays an important role in the development of high-performance systems,but extremely complicated reactions are involved.Because these complex phenomena are also bottlenecks for the establishment of all-sol id-state batteries(ASSB),we conducted multi-scale analysis using combined multi-measurement techniques,to directly observe charge/discharge reactions at hierarchical scales for the oxide-type ASSB using Na as the carrier cation.In particular,all of measurement techniques are applied to cross-section ASSB in the same cell,to complementarily evaluate the elemental distributions and structural changes.From Operando scanning electron microscopy-energy-dispersive X-ray spectroscopy,the Na concentration in the electrode layers changes on the micrometer scale under charge/discharge reactions in the first cycle.Furthermore,Operando Raman spectroscopy reveal changes in the bonding states at the atomic scale in the active material,including changes in reversible structural changes.After cycling the ASSB,the elemental distributions are clearly observed along with the particle shapes and can reveal the Na migration mechanism at the nanometer scale,by time-of-flight secondary ion mass spectrometry.Therefore,this study can provide a fundamental and comprehensive understanding of the charge/discharge mechanism by observing reaction processes at multiple scales.展开更多
Cement production,while essential for global infrastructure,contributes significantly to carbon dioxide emissions,accounting for approximately 7%of total emissions.To mitigate these environmental impacts,flash calcina...Cement production,while essential for global infrastructure,contributes significantly to carbon dioxide emissions,accounting for approximately 7%of total emissions.To mitigate these environmental impacts,flash calcination of kaolinitic clays has been investigated as a sustainable alternative.This technique involves the rapid heating of clays,enabling their use as supplementary cementitious materials.The primary objective of this study was to modify the color of calcined clay in various atmospheres(oxidizing,inert,and reducing)to achieve a grayish tone similar to commercial cement while preserving its reactive properties.The experimental procedure employed a tubular reactor with precise control of gas flows(atmospheric air,nitrogen,and a carbon monoxide–nitrogen mixture).Physicochemical characterization of the raw clay was conducted before calcination,with analyses repeated on the calcined clays following experimentation.Results indicated that clay calcined in an oxidizing atmosphere acquired a reddish hue,attributed to the oxidation of iron in hematite.The Clay exhibited a pinkish tone in an inert atmosphere,while calcination in a reducing atmosphere yielded the desired grayish color.Regarding pozzolanic activity,clays calcined in oxidizing and inert atmospheres displayed robust strength,ranging from 82%to 87%.Calcination in a reducing atmosphere resulted in slightly lower strength,around 74%,likely due to the clay’s chemical composition and the calcination process,which affects compound formation and material reactivity.展开更多
Earth-abundant copper and iron-mixed oxide(CuO/CuFeO_2; CFO) film electrodes are synthesized using an electrochemical deposition(ED) technique at two different ED potentials(-0.36 and-0.66 V vs saturated calomel ...Earth-abundant copper and iron-mixed oxide(CuO/CuFeO_2; CFO) film electrodes are synthesized using an electrochemical deposition(ED) technique at two different ED potentials(-0.36 and-0.66 V vs saturated calomel electrode(SCE); denoted as ED-1 and ED-2, respectively). Then, their surface morphologies are compared, and the photo(electro)catalytic activities for the reduction of Cr(VI) are examined in aqueous solutions at pH 7 under simulated sunlight(AM 1.5 G; 100 mW cm(-2)). The degree of the electrical potential applied to the ED process significantly affects the thickness of the synthesized electrode film and the intensity ratio of the diffraction peaks of CuO(111) and CuFeO_2(012). A 200 μm thick ED-2 sample with a distinct stacking of CuO on CuFeO_2 exhibits a larger broadband absorption spectrum than the 50-μm thick ED-1 with less separate stacking. Furthermore, the ED-2 sample has a higher intensity ratio of the diffraction peaks of CuO(111) and CuFe02(012) than ED-1. As-synthesized ED-2 samples produce larger photocurrents, leading to faster Cr(VI) reduction on the surface under given potential bias(-0.5 V vs SCE)or bias-free conditions. The energy levels(i.e., flatband potential) for the two samples are almost the same(only 10 mV difference), presumably supposing that the enhanced photoactivity of the ED-2 sample for Cr(VI) reduction is due to the facilitated charge transfer. The time-resolved photoluminescence emission spectra analysis reveal that the lifetime(r) of the charge carriers in the ED-1 sample is 0.103 ns, which decreases to 0.0876 ns in the ED-2. The ED-2 sample synthesized at a high negative potential is expected to contribute greatly to the application of other solar-to-fuel energy conversion fields as a highly efficient electrode material.展开更多
A novel rapid and continuous process has developed for the synthesis of nitrogen-doped TiO2(N-TiO2)with flame spray pyrolysis(FSP) method. The nitrogen incorporation into TiO2 was achieved by a facile modification...A novel rapid and continuous process has developed for the synthesis of nitrogen-doped TiO2(N-TiO2)with flame spray pyrolysis(FSP) method. The nitrogen incorporation into TiO2 was achieved by a facile modification(addition of dilute nitric acid) in the precursor for the synthesis. The catalysts were characterized by X-ray diffraction, Raman spectroscopy, transmission electron microscopy, diffuse reflectance spectroscopy, and X-ray photoelectron spectroscopy. The doping of nitrogen into the TiO2 was confirmed by X-ray photoelectron spectroscopy(XPS) and energy dispersive X-ray(EDX) spectroscopy. The UV-vis spectra of the modified catalysts(with primary N source) exhibited band-gap narrowing for 4 N-TiO2 with band gap energy of 2.89 eV, which may be due to the presence of nitrogen in TiO2 structure. The introduction of secondary N-source(urea) into TiO2 crystal lattice results in additional reduction of the band gap energy to 2.68 eV and shows a significant improvement of visible light absorption. The N-TiO2 nanoparticles modified by using secondary N-source showed significant photocatalytic activity under visible light much higher than TiO2. The higher activity is attributed to the synergetic interaction of nitrogen with the TiO2 lattice. The lowering of the band-gap energy for the flame made N-doped TiO2 materials implies that the nitrogen doping in TiO2 by aerosol method is highly effective in extending the optical response of TiO2 in the visible region. The nitrogen atomic percentage has increased monotonically(0.09%-0.15%)with the increase in primary nitrogen source(nitric acid), and significantly boosted to 0.97% when secondary nitrogen source(urea) was introduced. The highest rate of phenol degradation was obtained for catalysts with secondary N source due to increase in N content in the catalyst.展开更多
This study investigates the removal of arsenite(As(III)) from water using dithionite activated by UV light. This work evaluated the removal kinetics of As(III) under UV light irradiation as affected by dithionit...This study investigates the removal of arsenite(As(III)) from water using dithionite activated by UV light. This work evaluated the removal kinetics of As(III) under UV light irradiation as affected by dithionite dose and light intensity, and characterized the nature of the precipitated solids using XPS and SEM-EDS. Photolysis of dithionite was observed by measuring dithionite concentration using UV absorbance at 315 nm. This study also investigated the effect of UV light path length on soluble As concentrations to understand resolubilization mechanisms. Total soluble As concentrations were observed to decrease with reaction time due to reduction of arsenite to form solids having a yellow-orange color.The removal mechanism was found to be reductive precipitation that formed solids of elemental arsenic or arsenic sulfide. However, these solids were observed to resolubilize at later times after dithionite had been consumed. Resolubilization of As was prevented and additional As removal was obtained by frequent dosing of dithionite throughout the experiment. As(III) removal is attributed to photolysis of dithionite by UV light and production of reactive radicals that reduce As(III) and convert it to solid forms.展开更多
The present work explores the application of microwave heating for the melting of powdered tin. The mor- phology and particle size of powdered tin prepared by the centrifugal atomization method were charac- terized. T...The present work explores the application of microwave heating for the melting of powdered tin. The mor- phology and particle size of powdered tin prepared by the centrifugal atomization method were charac- terized. The tin particles were uniform and spherical in shape, with 90% of the particles in the size range of 38-75μm. The microwave absorption characteristic of the tin powder was assessed by an estimation of the dielectric properties. Microwave penetration was found to have good volumetric heating on powdered tin. Conduction losses were the main loss mechanisms for powdered tin by microwave heating at temperatures above 150 ℃. A 20 kW commercial-scale microwave tin-melting unit was designed, developed, and utilized for production. This unit achieved a heating rate that was at least 10 times higher than those of conventional methods, as well as a far shorter melting duration. The results suggest that microwave heating accelerates the heating rate and shortens the melting time. Tin recovery rate was 97.79%, with a slag ratio of only 1.65% and other losses accounting for less than 0.56%. The unit energy consumption was only 0.17 (kW·h)·kg-1- far lower than the energy required by conventional melting methods. Thus, the microwave melting process improved heating efficiency and reduced energy consumption.展开更多
The technology that waste activated carbon after extracting gold is regenerated with steam under microwave heating was studied. The influence of the activation temperature, activation duration and steam flow rate on i...The technology that waste activated carbon after extracting gold is regenerated with steam under microwave heating was studied. The influence of the activation temperature, activation duration and steam flow rate on iodine adsorption value and regeneration yield of activated carbon was investigated. The response surface methodology (RSM) technique was utilized to optimize the process conditions. The optimum conditions for the preparation of activated carbon are identified to be activation temperature of 831 ℃, activation duration of 40 min and steam flow rate of 2.67 mL/min. The optimum conditions result in an activated carbon with an iodine number of 1048 mg/g and a yield of 40%, and the BET surface area evaluated using nitrogen adsorption isotherm is 1493 m2/g, with total pore volume of 1.242 cm3/g. And the pore structure of activated carbon regenerated is mainly composed of micropores and a small amount of mesopores.展开更多
The central composite process optimization was performed by response surface methodology technique using a design for the treatment of methyltin mercaptide with modified semi-coke. The semi-coke from the coal industry...The central composite process optimization was performed by response surface methodology technique using a design for the treatment of methyltin mercaptide with modified semi-coke. The semi-coke from the coal industry was suitably modified by treating it with phosphoric acid, with a thermal activation process. The objective of the process optimization is to reduce the chemical oxygen demand (COD) and NH4+-N in the methyltin mercaptide industrial effluent. The process variables considered for process optimization are the semi-coke dosage, adsorption time and effluent pH. The optimized process conditions are identified to be a semi-coke dosage of 80 g/L, adsorption time of 90 min and a pH value of 8.34. The ANOVA results indicate that the adsorbent dosage and pH are the significant parameters, while the adsorption time is insignificant, possibly owing to the large range of adsorption time chosen. The textural characteristics of modified semi-coke were analyzed using scanning electron microscopy and nitrogen adsorption isotherm. The average BET surface area of modified semi-coke is estimated to be 915 mE/g, with the average pore volume of 0.71 cm3/g and a average pore diameter of 3.09 nm, with micropore volume contributing to 52.36%.展开更多
This paper proposes the use of the flexible tolerance method(FTM) modified with scaling of variables and hybridized with different unconstrained optimization methods to solve real constrained optimization problems.The...This paper proposes the use of the flexible tolerance method(FTM) modified with scaling of variables and hybridized with different unconstrained optimization methods to solve real constrained optimization problems.The benchmark problems used to analyze the performance of the methods were taken from G-Suite functions.The original method(FTM) and other four proposed methods:(i) FTM with scaling of variables(FTMS),(ii) FTMS hybridized with BFGS(FTMS-BFGS),(iii) FTMS hybridized with modified Powell's method(FTMS-Powell)and(iv) FTMS hybridized with PSO(FTMS-PSO), were implemented. The success rates of the methods were 80%,100%, 75%, 95% and 85%, for FTM, FTMS, FTMS-BFGS, FTMS-Powell and FTMS-PSO, respectively. Numerical experiments including real constrained problems indicated that FTMS gave the best performance, followed by FTMSPowell and FTMS-PSO. Despite the inferior performance compared to FTMS and FTMS-Powell, the FTMS-PSO method presented some advantages since good different initial points could be obtained, which allow exploring different routes through the solution space and to escape from local optima. The proposed methods proved to be an effective way of improving the performance of the original FTM.展开更多
Inferential models are widely used in the chemical industry to infer key process variables, which are challenging or expensive to measure, from other more easily measured variables. The aim of this paper is three-fold...Inferential models are widely used in the chemical industry to infer key process variables, which are challenging or expensive to measure, from other more easily measured variables. The aim of this paper is three-fold: to present a theoretical review of some of the well known linear inferential modeling techniques, to enhance the predictive ability of the regularized canonical correlation analysis (RCCA) method, and finally to compare the performances of these techniques and highlight some of the practical issues that can affect their predictive abilities. The inferential modeling techniques considered in this study include full rank modeling techniques, such as ordinary least square (OLS) regression and ridge regression (RR), and latent variable regression (LVR) techniques, such as principal component regression (PCR), partial least squares (PLS) regression, and regularized canonical correlation analysis (RCCA). The theoretical analysis shows that the loading vectors used in LVR modeling can be computed by solving eigenvalue problems. Also, for the RCCA method, we show that by optimizing the regularization parameter, an improvement in prediction accuracy can be achieved over other modeling techniques. To illustrate the performances of all inferential modeling techniques, a comparative analysis was performed through two simulated examples, one using synthetic data and the other using simulated distillation column data. All techniques are optimized and compared by computing the cross validation mean square error using unseen testing data. The results of this comparative analysis show that scaling the data helps improve the performances of all modeling techniques, and that the LVR techniques outperform the full rank ones. One reason for this advantage is that the LVR techniques improve the conditioning of the model by discarding the latent variables (or principal components) with small eigenvalues, which also reduce the effect of the noise on the model prediction. The results also show that PCR and PLS have comparable performances, and that RCCA can provide an advantage by optimizing its regularization parameter.展开更多
This paper proposes the use of the flexible tolerance method(FTM) modified with adaptive Nelder–Mead parameters and barrier to solve constrained optimization problems. The problems used to analyze the performance of ...This paper proposes the use of the flexible tolerance method(FTM) modified with adaptive Nelder–Mead parameters and barrier to solve constrained optimization problems. The problems used to analyze the performance of the methods were taken from G-Suite functions, and the methods with the best performance were applied in mass integration problems. Four methods were proposed:(1) flexible tolerance method(FTM) using adaptive parameters(FTMA),(2) flexible tolerance method with scaling(FTMS) and with adaptive parameters(FTMAS),(3) FTMS including the barrier modification(MFTMS) and(4) MFTMS hybridized with PSO(MFTMS-PSO). The success rates of these methods were 100%(MFTMS), 85%(MFTMS-PSO), 40%(FTMAS) and 30%(FTMA).Numerical experiments indicated that the MFTMS could efficiently and reliably improve the accuracy of global optima. In mass integration, the method was able, from current process situation, to reach the optimum process configuration that includes integration issues, which was not possible using FTM in its standard formulation. The hybridization of FTMS with PSO(without barrier), FTMS-PSO, was also able to solve mass integration problems efficiently.展开更多
Recent years have seen notable progress in the use of deep eutectic solvents(DESs)in pharmaceutical applications.This is ascribed to the high preparation flexibility of DES mixtures and the ability tomulti-tune their ...Recent years have seen notable progress in the use of deep eutectic solvents(DESs)in pharmaceutical applications.This is ascribed to the high preparation flexibility of DES mixtures and the ability tomulti-tune their physicochemical properties and biopharmaceutical characteristics.The aim of this article is to provide perspective concerning the applications of DESs in pharmaceutical systems and their potential based on the current state of the field.Notably,there is some disagreement about whether some mixtures are in fact DESs or ionic liquids(ILs)[1].This indicates the need for more robust standards and definitions so as to avoid confusion within the scientific community.Many studies consider DESs to either constitute a subclass of ILs,analogs of ILs,or alternatives to ILs.In this regard,it would be best for the IUPAC to standardize DES classification and their similarity/dissimilarity with ILs.展开更多
The interest in using therapeutic nanoparticles to bind with harmful molecules or pathogens and subsequently neutralize their bioactivity has grown tremendously.Among various nanomedicine platforms,cell membrane-coate...The interest in using therapeutic nanoparticles to bind with harmful molecules or pathogens and subsequently neutralize their bioactivity has grown tremendously.Among various nanomedicine platforms,cell membrane-coated nanoparticles,namely,“cellular nanosponges,”stand out for their broadspectrum neutralization capability challenging to achieve in traditional countermeasure technologies.Such ability is attributable to their cellular function-based rather than target structure-based working principle.Integrating cellular nanosponges with various synthetic substrates further makes their applications exceptionally versatile and adaptive.This review discusses the latest cellular nanosponge technology focusing on how the structure–function relationship in different designs has led to versatile and potent medical countermeasures.Four design strategies are discussed,including harnessing native cell membrane functions for biological neutralization,functionalizing cell membrane coatings to enhance neutralization capabilities,combining cell membranes and functional cores for multimodal neutralization,and integrating cellular nanosponges with hydrogels for localized applications.Examples in each design strategy are selected,and the discussion is to highlight their structure–function relationships in complex disease settings.The review may inspire additional design strategies for cellular nanosponges and fulfill even broader medical applications.展开更多
The utilization of supercritical fluids (SCF) in the Fischer-Tropsch Synthesis (FTS) further complicates the hydrocarbon products identification and analysis process due to the dilution of hydrocarbon peaks by the pre...The utilization of supercritical fluids (SCF) in the Fischer-Tropsch Synthesis (FTS) further complicates the hydrocarbon products identification and analysis process due to the dilution of hydrocarbon peaks by the predominant solvent peak. Therefore, in this project, a custom-made Gas Chromatography (GC) analysis system was designed and implemented to identify and quantify SCF-FTS products. The FTS products were identified using two different methods. The first was through retention time matching by injecting standard solutions, and the second was through the use of the GC/MS system. The quantification of CO and CH4 was achieved by using external standards, where the CO conversion was calculated by relating the peak area of CO to the peak area of an internal standard (argon) while the CH4 selectivity was calculated by relating the peak area of CH4 to that of CO. After setting and calibrating the GC system, two reaction conditions (gas phase: 240°C, 20 bar syngas with 2:1 H2:CO molar feed ratio and for the supercritical fluids FTS (SCF-FTS): 240°C, 65 bar with 20 bar syngas partial pressure and 2:1 H2:CO molar feed ratio) were used to compare the different FTS reaction media. The comparison between the gas phase FTS and the SCF-FTS showed the following: carbon monoxide conversion was improved by 14% in the SCF-FTS, while the hydrocarbon product profile SCF-FTS showed 78% reduction in light hydrocarbons (C1 - C4) products, 35% increase in middle distillates (C11 - C22) products compared to gas phase FTS. These improvements have resulted in higher chain growth probability for the SCF-FTS (α = 0.85) compared to the gas phase FTS (α = 0.76). These results are generally in agreement with previously reported enhancement in the SCF-FTS[1].展开更多
While reliance on renewable energy resources has become a reality, there is still a need to deploy greener and more sustainable methods in order to achieve sustainable development goals. Indeed, green hydrogen is curr...While reliance on renewable energy resources has become a reality, there is still a need to deploy greener and more sustainable methods in order to achieve sustainable development goals. Indeed, green hydrogen is currently believed to be a reliable solution for global warming and the pollution challenges arising from fossil fuels, making it the resilient fuel of the future. However, the sustainability of green hydrogen technologies is yet to be achieved. In this context, generation of green hydrogen with the aid of deep eutectic solvents(DESs) as green mixtures has been demonstrated as a promising research area. This systematic review article covers green hydrogen generation through water splitting and biomass fermentation when DESs are utilized within the generation process. It also discusses the incorporation of DESs in fuel cell technologies. DESs can play a variety of roles such as solvent, electrolyte, or precursor;colloidal suspension and reaction medium;galvanic replacement, shape-controlling, decoration, or extractive agent;finally oxidant. These roles are relevant to several methods of green hydrogen generation, including electrocatalysis, photocatalysis, and fermentation. As such, it is of utmost importance to screen potential DES formulations and determine how they can function in and contribute throughout the green hydrogen mobility stages. The realization of super green hydrogen generation stands out as a pivotal milestone in our journey towards achieving a more sustainable form of development;DESs have great potential in making this milestone achievable. Overall, incorporating DESs in hydrogen generation constitutes a promising research area and offers potential scalability for green hydrogen production, storage,transport, and utilization.展开更多
Given their dangerous effects on the nervous system,neurotoxins represent a significant threat to public health.Various therapeutic approaches,including chelating agents,receptor decoys,and toxin-neutralizing antibodi...Given their dangerous effects on the nervous system,neurotoxins represent a significant threat to public health.Various therapeutic approaches,including chelating agents,receptor decoys,and toxin-neutralizing antibodies,have been explored.While prophylactic vaccines are desirable,it is oftentimes difficult to effectively balance their safety and efficacy given the highly dangerous nature of neurotoxins.To address this,we report here on a nanovaccine against neurotoxins that leverages the detoxifying properties of cell membrane-coated nanoparticles.A genetically modified cell line with constitutive overexpression of theα7 nicotinic acetylcholine receptor is developed as a membrane source to generate biomimetic nanoparticles that can effectively and irreversibly bind toα-bungarotoxin,a model neurotoxin.This abrogates the biological activity of the toxin,enabling the resulting nanotoxoid to be safely delivered into the body and processed by the immune system.When co-administered with an immunological adjuvant,a strong humoral response againstα-bungarotoxin is generated that protects vaccinated mice against a lethal dose of the toxin.Overall,this work highlights the potential of using genetic modification strategies to develop nanotoxoid formulations against various biological threats.展开更多
This study investigates the detailed mechanism of CO_(2) conversion to CO using the manganese(I) diimine electrocatalyst [Mn(pyrox)(CO)3Br], synthesized by Christoph Steinlechner and coworkers. Employing density funct...This study investigates the detailed mechanism of CO_(2) conversion to CO using the manganese(I) diimine electrocatalyst [Mn(pyrox)(CO)3Br], synthesized by Christoph Steinlechner and coworkers. Employing density functional theory calculations, we thoroughly explore the electrocatalytic pathway of CO_(2) reduction alongside the competing hydrogen evolution reaction. Our analysis reveals the significant role of diimine nitrogen coordination in enhancing the electron density of the Mn center, thereby favoring both CO_(2) reduction and hydrogen evolution reaction thermodynamically. Furthermore, we observe that triethanolamine (TEOA) stabilizes transition states, aiding in CO_(2) fixation and reduction. The critical steps influencing the reaction rate involve breaking the MnC(O)–OH bond during CO_(2) reduction and cleaving the MnH–H–TEOA bond in the hydrogen evolution reaction. We explain the preference for CO_(2) conversion to CO over H_(2) evolution due to the higher energy barrier in forming the Mn-H_(2) species during H_(2) production. Our findings suggest the potential for tuning the electron density of the Mn center to enhance reactivity and selectivity in CO_(2) reduction. Additionally, we analyze potential competing reactions, focusing on electrocatalytic processes for CO_(2) reduction and evaluating “protonation-first” and “reduction-first” pathways through density functional theory calculations of redox potentials and Gibbs free energies. This analysis indicates the predominance of the “reduction-first” pathway in CO production, especially under high applied potential conditions. Moreover, our research highlights the selectivity of [Mn(pyrox)(CO)3Br] toward CO production over HCOO– and H_(2) formation, proposing avenues for future research to expand upon these findings by using larger basis sets and exploring additional functionalized ligands.展开更多
Inflammatory cytokines are key players in modulating immune responses to mount effective host defense.However,excessive production of inflammatory cytokines contributes to the destructive components responsible for va...Inflammatory cytokines are key players in modulating immune responses to mount effective host defense.However,excessive production of inflammatory cytokines contributes to the destructive components responsible for various inflammatory disorders.As a result,treatment strategies have been developed to lower the cytokine levels or block their bioactivity.In particular,therapeutic agents that directly capture and neutralize cytokines have gained significant attention as they bypass the interactions with the host cells,and therefore,are less likely to induce immunogenic response and clearance.Among them,“monoplex”platforms such as cytokine-neutralizing antibodies(CNAs)are commonly designed to target a specific cytokine for neutralization.Meanwhile,to address the multiplexity of the cytokine targets in diseases,multiplex platforms such as glycosaminoglycan-containing biomaterials and cell-membrane-coated nanoparticles are emerging.Herein,we have reviewed the recent progress of these cytokine-neutralizing platforms(CNPs)and discussed their applications in treating inflammatory disorders.Overall,understanding the structure–function relationships underlying these CNPs would lead to the design of novel therapeutics toward effective management of inflammatory diseases.展开更多
With tremendous research advances in biomedical application,liquid metals(LM)also offer fantastic chemistry for synthesis of novel nano-composites.Herein,as a pioneering trial,litchi-shaped heterogeneous eutectic gall...With tremendous research advances in biomedical application,liquid metals(LM)also offer fantastic chemistry for synthesis of novel nano-composites.Herein,as a pioneering trial,litchi-shaped heterogeneous eutectic gallium indium-Au nanoparticles(EGaIn-Au NPs),served as effective radiosensitizer and photothermal agent for radio-photothermal cancer therapy,have been successfully prepared using in situ interfacial galvanic replacement reaction.The enhanced photothermal conversion efficiency and boosted radio-sensitization effect could be achieved with the reduction of Au nanodots onto the eutectic gallium indium(EGaIn)NPs surface.Most importantly,the growth of tumor could be effectively inhibited under the combined radio-photothermal therapy mediated by EGaIn-Au NPs.Inspired by this approach,in situ interfacial galvanic replacement reaction may open a novel strategy to fabricate LM-based nano-composite with advanced multi-functionalities.展开更多
基金the Ministry of Higher Education,Research and Innovation-Oman for their support of this research through TRC block funding grant No.BFP/RGP/EBR/22/378.
文摘Innately designed to induce physiological changes,pharmaceuticals are foreknowingly hazardous to the ecosystem.Advanced oxidation processes(AOPs)are recognized as a set of contemporary and highly efficient methods being used as a contrivance for the removal of pharmaceutical residues.Since reactive oxygen species(ROS)are formed in these processes to interact and contribute directly toward the oxidation of target contaminant(s),a profound insight regarding the mechanisms of ROS leading to the degradation of pharmaceuticals is fundamentally significant.The conceptualization of some specific reaction mechanisms allows the design of an effective and safe degradation process that can empirically reduce the environmental impact of themicropollutants.This review mainly deliberates themechanistic reaction pathways for ROS-mediated degradation of pharmaceuticals often leading to complete mineralization,with a focus on acetaminophen as a drug waste model.
基金This article is based on results obtained from a project,Grant JPNP14004,commissioned by the New Energy and Industrial Technology Development Organization(NEDO)。
文摘Understanding the charge/discharge mechanism of batteries plays an important role in the development of high-performance systems,but extremely complicated reactions are involved.Because these complex phenomena are also bottlenecks for the establishment of all-sol id-state batteries(ASSB),we conducted multi-scale analysis using combined multi-measurement techniques,to directly observe charge/discharge reactions at hierarchical scales for the oxide-type ASSB using Na as the carrier cation.In particular,all of measurement techniques are applied to cross-section ASSB in the same cell,to complementarily evaluate the elemental distributions and structural changes.From Operando scanning electron microscopy-energy-dispersive X-ray spectroscopy,the Na concentration in the electrode layers changes on the micrometer scale under charge/discharge reactions in the first cycle.Furthermore,Operando Raman spectroscopy reveal changes in the bonding states at the atomic scale in the active material,including changes in reversible structural changes.After cycling the ASSB,the elemental distributions are clearly observed along with the particle shapes and can reveal the Na migration mechanism at the nanometer scale,by time-of-flight secondary ion mass spectrometry.Therefore,this study can provide a fundamental and comprehensive understanding of the charge/discharge mechanism by observing reaction processes at multiple scales.
基金financial support for the research and for the publication costs of the articlesupported by Santa Catarina State Research Support Foundation(FAPESC)National Council for Scientific and Technological Development(CNPq no 302903/2023-2).
文摘Cement production,while essential for global infrastructure,contributes significantly to carbon dioxide emissions,accounting for approximately 7%of total emissions.To mitigate these environmental impacts,flash calcination of kaolinitic clays has been investigated as a sustainable alternative.This technique involves the rapid heating of clays,enabling their use as supplementary cementitious materials.The primary objective of this study was to modify the color of calcined clay in various atmospheres(oxidizing,inert,and reducing)to achieve a grayish tone similar to commercial cement while preserving its reactive properties.The experimental procedure employed a tubular reactor with precise control of gas flows(atmospheric air,nitrogen,and a carbon monoxide–nitrogen mixture).Physicochemical characterization of the raw clay was conducted before calcination,with analyses repeated on the calcined clays following experimentation.Results indicated that clay calcined in an oxidizing atmosphere acquired a reddish hue,attributed to the oxidation of iron in hematite.The Clay exhibited a pinkish tone in an inert atmosphere,while calcination in a reducing atmosphere yielded the desired grayish color.Regarding pozzolanic activity,clays calcined in oxidizing and inert atmospheres displayed robust strength,ranging from 82%to 87%.Calcination in a reducing atmosphere resulted in slightly lower strength,around 74%,likely due to the clay’s chemical composition and the calcination process,which affects compound formation and material reactivity.
基金financially supported by the National Priorities Research Program (NPRP) award (No. NPRP 7-865-2-320) from the Qatar National Research Fund (QNRF) (a member of the Qatar Foundation)the Nano-Material Technology Development Program (No. NRF-2016M3A7B4908169),Korea,for its financial support
文摘Earth-abundant copper and iron-mixed oxide(CuO/CuFeO_2; CFO) film electrodes are synthesized using an electrochemical deposition(ED) technique at two different ED potentials(-0.36 and-0.66 V vs saturated calomel electrode(SCE); denoted as ED-1 and ED-2, respectively). Then, their surface morphologies are compared, and the photo(electro)catalytic activities for the reduction of Cr(VI) are examined in aqueous solutions at pH 7 under simulated sunlight(AM 1.5 G; 100 mW cm(-2)). The degree of the electrical potential applied to the ED process significantly affects the thickness of the synthesized electrode film and the intensity ratio of the diffraction peaks of CuO(111) and CuFeO_2(012). A 200 μm thick ED-2 sample with a distinct stacking of CuO on CuFeO_2 exhibits a larger broadband absorption spectrum than the 50-μm thick ED-1 with less separate stacking. Furthermore, the ED-2 sample has a higher intensity ratio of the diffraction peaks of CuO(111) and CuFe02(012) than ED-1. As-synthesized ED-2 samples produce larger photocurrents, leading to faster Cr(VI) reduction on the surface under given potential bias(-0.5 V vs SCE)or bias-free conditions. The energy levels(i.e., flatband potential) for the two samples are almost the same(only 10 mV difference), presumably supposing that the enhanced photoactivity of the ED-2 sample for Cr(VI) reduction is due to the facilitated charge transfer. The time-resolved photoluminescence emission spectra analysis reveal that the lifetime(r) of the charge carriers in the ED-1 sample is 0.103 ns, which decreases to 0.0876 ns in the ED-2. The ED-2 sample synthesized at a high negative potential is expected to contribute greatly to the application of other solar-to-fuel energy conversion fields as a highly efficient electrode material.
基金the U.S. EPA/Pegasus contract (contract number EP-C-11-006) for financial support of this work through the scholarship to Siva Nagi Reddy Inturi
文摘A novel rapid and continuous process has developed for the synthesis of nitrogen-doped TiO2(N-TiO2)with flame spray pyrolysis(FSP) method. The nitrogen incorporation into TiO2 was achieved by a facile modification(addition of dilute nitric acid) in the precursor for the synthesis. The catalysts were characterized by X-ray diffraction, Raman spectroscopy, transmission electron microscopy, diffuse reflectance spectroscopy, and X-ray photoelectron spectroscopy. The doping of nitrogen into the TiO2 was confirmed by X-ray photoelectron spectroscopy(XPS) and energy dispersive X-ray(EDX) spectroscopy. The UV-vis spectra of the modified catalysts(with primary N source) exhibited band-gap narrowing for 4 N-TiO2 with band gap energy of 2.89 eV, which may be due to the presence of nitrogen in TiO2 structure. The introduction of secondary N-source(urea) into TiO2 crystal lattice results in additional reduction of the band gap energy to 2.68 eV and shows a significant improvement of visible light absorption. The N-TiO2 nanoparticles modified by using secondary N-source showed significant photocatalytic activity under visible light much higher than TiO2. The higher activity is attributed to the synergetic interaction of nitrogen with the TiO2 lattice. The lowering of the band-gap energy for the flame made N-doped TiO2 materials implies that the nitrogen doping in TiO2 by aerosol method is highly effective in extending the optical response of TiO2 in the visible region. The nitrogen atomic percentage has increased monotonically(0.09%-0.15%)with the increase in primary nitrogen source(nitric acid), and significantly boosted to 0.97% when secondary nitrogen source(urea) was introduced. The highest rate of phenol degradation was obtained for catalysts with secondary N source due to increase in N content in the catalyst.
基金possible by grants from the Qatar National Research Fund under its National Priorities Research Program award number NPRP 6-729-2-301 and NPRP 8-1406-2-605
文摘This study investigates the removal of arsenite(As(III)) from water using dithionite activated by UV light. This work evaluated the removal kinetics of As(III) under UV light irradiation as affected by dithionite dose and light intensity, and characterized the nature of the precipitated solids using XPS and SEM-EDS. Photolysis of dithionite was observed by measuring dithionite concentration using UV absorbance at 315 nm. This study also investigated the effect of UV light path length on soluble As concentrations to understand resolubilization mechanisms. Total soluble As concentrations were observed to decrease with reaction time due to reduction of arsenite to form solids having a yellow-orange color.The removal mechanism was found to be reductive precipitation that formed solids of elemental arsenic or arsenic sulfide. However, these solids were observed to resolubilize at later times after dithionite had been consumed. Resolubilization of As was prevented and additional As removal was obtained by frequent dosing of dithionite throughout the experiment. As(III) removal is attributed to photolysis of dithionite by UV light and production of reactive radicals that reduce As(III) and convert it to solid forms.
文摘The present work explores the application of microwave heating for the melting of powdered tin. The mor- phology and particle size of powdered tin prepared by the centrifugal atomization method were charac- terized. The tin particles were uniform and spherical in shape, with 90% of the particles in the size range of 38-75μm. The microwave absorption characteristic of the tin powder was assessed by an estimation of the dielectric properties. Microwave penetration was found to have good volumetric heating on powdered tin. Conduction losses were the main loss mechanisms for powdered tin by microwave heating at temperatures above 150 ℃. A 20 kW commercial-scale microwave tin-melting unit was designed, developed, and utilized for production. This unit achieved a heating rate that was at least 10 times higher than those of conventional methods, as well as a far shorter melting duration. The results suggest that microwave heating accelerates the heating rate and shortens the melting time. Tin recovery rate was 97.79%, with a slag ratio of only 1.65% and other losses accounting for less than 0.56%. The unit energy consumption was only 0.17 (kW·h)·kg-1- far lower than the energy required by conventional melting methods. Thus, the microwave melting process improved heating efficiency and reduced energy consumption.
基金Project(2013AA064003)supported by the National High Technology Research and Development Program of ChinaProject(2012HB008)supported by Young and Middle-aged Academic Technology Leader Backup Talent Cultivation Program in Yunnan Province,China
文摘The technology that waste activated carbon after extracting gold is regenerated with steam under microwave heating was studied. The influence of the activation temperature, activation duration and steam flow rate on iodine adsorption value and regeneration yield of activated carbon was investigated. The response surface methodology (RSM) technique was utilized to optimize the process conditions. The optimum conditions for the preparation of activated carbon are identified to be activation temperature of 831 ℃, activation duration of 40 min and steam flow rate of 2.67 mL/min. The optimum conditions result in an activated carbon with an iodine number of 1048 mg/g and a yield of 40%, and the BET surface area evaluated using nitrogen adsorption isotherm is 1493 m2/g, with total pore volume of 1.242 cm3/g. And the pore structure of activated carbon regenerated is mainly composed of micropores and a small amount of mesopores.
基金Projects(5114703,51004059/E041601)supported by the National Natural Science Foundation of China
文摘The central composite process optimization was performed by response surface methodology technique using a design for the treatment of methyltin mercaptide with modified semi-coke. The semi-coke from the coal industry was suitably modified by treating it with phosphoric acid, with a thermal activation process. The objective of the process optimization is to reduce the chemical oxygen demand (COD) and NH4+-N in the methyltin mercaptide industrial effluent. The process variables considered for process optimization are the semi-coke dosage, adsorption time and effluent pH. The optimized process conditions are identified to be a semi-coke dosage of 80 g/L, adsorption time of 90 min and a pH value of 8.34. The ANOVA results indicate that the adsorbent dosage and pH are the significant parameters, while the adsorption time is insignificant, possibly owing to the large range of adsorption time chosen. The textural characteristics of modified semi-coke were analyzed using scanning electron microscopy and nitrogen adsorption isotherm. The average BET surface area of modified semi-coke is estimated to be 915 mE/g, with the average pore volume of 0.71 cm3/g and a average pore diameter of 3.09 nm, with micropore volume contributing to 52.36%.
基金CAPES(Coordenacao de Aperfeicoamento de Pessoal de Nível Superior)CNPq(Conselho Nacional de Desenvolvimento Científicoe Tecnológico,grant number 161464/2013-0)for the financial support
文摘This paper proposes the use of the flexible tolerance method(FTM) modified with scaling of variables and hybridized with different unconstrained optimization methods to solve real constrained optimization problems.The benchmark problems used to analyze the performance of the methods were taken from G-Suite functions.The original method(FTM) and other four proposed methods:(i) FTM with scaling of variables(FTMS),(ii) FTMS hybridized with BFGS(FTMS-BFGS),(iii) FTMS hybridized with modified Powell's method(FTMS-Powell)and(iv) FTMS hybridized with PSO(FTMS-PSO), were implemented. The success rates of the methods were 80%,100%, 75%, 95% and 85%, for FTM, FTMS, FTMS-BFGS, FTMS-Powell and FTMS-PSO, respectively. Numerical experiments including real constrained problems indicated that FTMS gave the best performance, followed by FTMSPowell and FTMS-PSO. Despite the inferior performance compared to FTMS and FTMS-Powell, the FTMS-PSO method presented some advantages since good different initial points could be obtained, which allow exploring different routes through the solution space and to escape from local optima. The proposed methods proved to be an effective way of improving the performance of the original FTM.
文摘Inferential models are widely used in the chemical industry to infer key process variables, which are challenging or expensive to measure, from other more easily measured variables. The aim of this paper is three-fold: to present a theoretical review of some of the well known linear inferential modeling techniques, to enhance the predictive ability of the regularized canonical correlation analysis (RCCA) method, and finally to compare the performances of these techniques and highlight some of the practical issues that can affect their predictive abilities. The inferential modeling techniques considered in this study include full rank modeling techniques, such as ordinary least square (OLS) regression and ridge regression (RR), and latent variable regression (LVR) techniques, such as principal component regression (PCR), partial least squares (PLS) regression, and regularized canonical correlation analysis (RCCA). The theoretical analysis shows that the loading vectors used in LVR modeling can be computed by solving eigenvalue problems. Also, for the RCCA method, we show that by optimizing the regularization parameter, an improvement in prediction accuracy can be achieved over other modeling techniques. To illustrate the performances of all inferential modeling techniques, a comparative analysis was performed through two simulated examples, one using synthetic data and the other using simulated distillation column data. All techniques are optimized and compared by computing the cross validation mean square error using unseen testing data. The results of this comparative analysis show that scaling the data helps improve the performances of all modeling techniques, and that the LVR techniques outperform the full rank ones. One reason for this advantage is that the LVR techniques improve the conditioning of the model by discarding the latent variables (or principal components) with small eigenvalues, which also reduce the effect of the noise on the model prediction. The results also show that PCR and PLS have comparable performances, and that RCCA can provide an advantage by optimizing its regularization parameter.
基金CAPES(Coordenacao de Aperfeicoamento de Pessoal de Nível Superior)CNPq(Conselho Nacional de Desenvolvimento Científico e Tecnológico,grant number 161464/2013-0)for financial support.
文摘This paper proposes the use of the flexible tolerance method(FTM) modified with adaptive Nelder–Mead parameters and barrier to solve constrained optimization problems. The problems used to analyze the performance of the methods were taken from G-Suite functions, and the methods with the best performance were applied in mass integration problems. Four methods were proposed:(1) flexible tolerance method(FTM) using adaptive parameters(FTMA),(2) flexible tolerance method with scaling(FTMS) and with adaptive parameters(FTMAS),(3) FTMS including the barrier modification(MFTMS) and(4) MFTMS hybridized with PSO(MFTMS-PSO). The success rates of these methods were 100%(MFTMS), 85%(MFTMS-PSO), 40%(FTMAS) and 30%(FTMA).Numerical experiments indicated that the MFTMS could efficiently and reliably improve the accuracy of global optima. In mass integration, the method was able, from current process situation, to reach the optimum process configuration that includes integration issues, which was not possible using FTM in its standard formulation. The hybridization of FTMS with PSO(without barrier), FTMS-PSO, was also able to solve mass integration problems efficiently.
文摘Recent years have seen notable progress in the use of deep eutectic solvents(DESs)in pharmaceutical applications.This is ascribed to the high preparation flexibility of DES mixtures and the ability tomulti-tune their physicochemical properties and biopharmaceutical characteristics.The aim of this article is to provide perspective concerning the applications of DESs in pharmaceutical systems and their potential based on the current state of the field.Notably,there is some disagreement about whether some mixtures are in fact DESs or ionic liquids(ILs)[1].This indicates the need for more robust standards and definitions so as to avoid confusion within the scientific community.Many studies consider DESs to either constitute a subclass of ILs,analogs of ILs,or alternatives to ILs.In this regard,it would be best for the IUPAC to standardize DES classification and their similarity/dissimilarity with ILs.
基金This work is supported by the Defense Threat Reduction Agency Joint Science and Technology Office for Chemical and Biological Defense under Award Numbers HDTRA1-21-1-0010 and HDTRA1-21-C-0019.
文摘The interest in using therapeutic nanoparticles to bind with harmful molecules or pathogens and subsequently neutralize their bioactivity has grown tremendously.Among various nanomedicine platforms,cell membrane-coated nanoparticles,namely,“cellular nanosponges,”stand out for their broadspectrum neutralization capability challenging to achieve in traditional countermeasure technologies.Such ability is attributable to their cellular function-based rather than target structure-based working principle.Integrating cellular nanosponges with various synthetic substrates further makes their applications exceptionally versatile and adaptive.This review discusses the latest cellular nanosponge technology focusing on how the structure–function relationship in different designs has led to versatile and potent medical countermeasures.Four design strategies are discussed,including harnessing native cell membrane functions for biological neutralization,functionalizing cell membrane coatings to enhance neutralization capabilities,combining cell membranes and functional cores for multimodal neutralization,and integrating cellular nanosponges with hydrogels for localized applications.Examples in each design strategy are selected,and the discussion is to highlight their structure–function relationships in complex disease settings.The review may inspire additional design strategies for cellular nanosponges and fulfill even broader medical applications.
文摘The utilization of supercritical fluids (SCF) in the Fischer-Tropsch Synthesis (FTS) further complicates the hydrocarbon products identification and analysis process due to the dilution of hydrocarbon peaks by the predominant solvent peak. Therefore, in this project, a custom-made Gas Chromatography (GC) analysis system was designed and implemented to identify and quantify SCF-FTS products. The FTS products were identified using two different methods. The first was through retention time matching by injecting standard solutions, and the second was through the use of the GC/MS system. The quantification of CO and CH4 was achieved by using external standards, where the CO conversion was calculated by relating the peak area of CO to the peak area of an internal standard (argon) while the CH4 selectivity was calculated by relating the peak area of CH4 to that of CO. After setting and calibrating the GC system, two reaction conditions (gas phase: 240°C, 20 bar syngas with 2:1 H2:CO molar feed ratio and for the supercritical fluids FTS (SCF-FTS): 240°C, 65 bar with 20 bar syngas partial pressure and 2:1 H2:CO molar feed ratio) were used to compare the different FTS reaction media. The comparison between the gas phase FTS and the SCF-FTS showed the following: carbon monoxide conversion was improved by 14% in the SCF-FTS, while the hydrocarbon product profile SCF-FTS showed 78% reduction in light hydrocarbons (C1 - C4) products, 35% increase in middle distillates (C11 - C22) products compared to gas phase FTS. These improvements have resulted in higher chain growth probability for the SCF-FTS (α = 0.85) compared to the gas phase FTS (α = 0.76). These results are generally in agreement with previously reported enhancement in the SCF-FTS[1].
基金the Ministry of Higher Education,Research and Innovation(MoHERI)Oman for their support of this research through TRC block funding Grant no.:BFP/RGP/EBR/22/378。
文摘While reliance on renewable energy resources has become a reality, there is still a need to deploy greener and more sustainable methods in order to achieve sustainable development goals. Indeed, green hydrogen is currently believed to be a reliable solution for global warming and the pollution challenges arising from fossil fuels, making it the resilient fuel of the future. However, the sustainability of green hydrogen technologies is yet to be achieved. In this context, generation of green hydrogen with the aid of deep eutectic solvents(DESs) as green mixtures has been demonstrated as a promising research area. This systematic review article covers green hydrogen generation through water splitting and biomass fermentation when DESs are utilized within the generation process. It also discusses the incorporation of DESs in fuel cell technologies. DESs can play a variety of roles such as solvent, electrolyte, or precursor;colloidal suspension and reaction medium;galvanic replacement, shape-controlling, decoration, or extractive agent;finally oxidant. These roles are relevant to several methods of green hydrogen generation, including electrocatalysis, photocatalysis, and fermentation. As such, it is of utmost importance to screen potential DES formulations and determine how they can function in and contribute throughout the green hydrogen mobility stages. The realization of super green hydrogen generation stands out as a pivotal milestone in our journey towards achieving a more sustainable form of development;DESs have great potential in making this milestone achievable. Overall, incorporating DESs in hydrogen generation constitutes a promising research area and offers potential scalability for green hydrogen production, storage,transport, and utilization.
基金supported by the Defense Threat Reduction Agency Joint Science and Technology Office for Chemical and Biological Defense under award number HDTRA1-21-1-0010the National Institutes of Health under Award Numbers R21AI159492 and R21AI175904.
文摘Given their dangerous effects on the nervous system,neurotoxins represent a significant threat to public health.Various therapeutic approaches,including chelating agents,receptor decoys,and toxin-neutralizing antibodies,have been explored.While prophylactic vaccines are desirable,it is oftentimes difficult to effectively balance their safety and efficacy given the highly dangerous nature of neurotoxins.To address this,we report here on a nanovaccine against neurotoxins that leverages the detoxifying properties of cell membrane-coated nanoparticles.A genetically modified cell line with constitutive overexpression of theα7 nicotinic acetylcholine receptor is developed as a membrane source to generate biomimetic nanoparticles that can effectively and irreversibly bind toα-bungarotoxin,a model neurotoxin.This abrogates the biological activity of the toxin,enabling the resulting nanotoxoid to be safely delivered into the body and processed by the immune system.When co-administered with an immunological adjuvant,a strong humoral response againstα-bungarotoxin is generated that protects vaccinated mice against a lethal dose of the toxin.Overall,this work highlights the potential of using genetic modification strategies to develop nanotoxoid formulations against various biological threats.
文摘This study investigates the detailed mechanism of CO_(2) conversion to CO using the manganese(I) diimine electrocatalyst [Mn(pyrox)(CO)3Br], synthesized by Christoph Steinlechner and coworkers. Employing density functional theory calculations, we thoroughly explore the electrocatalytic pathway of CO_(2) reduction alongside the competing hydrogen evolution reaction. Our analysis reveals the significant role of diimine nitrogen coordination in enhancing the electron density of the Mn center, thereby favoring both CO_(2) reduction and hydrogen evolution reaction thermodynamically. Furthermore, we observe that triethanolamine (TEOA) stabilizes transition states, aiding in CO_(2) fixation and reduction. The critical steps influencing the reaction rate involve breaking the MnC(O)–OH bond during CO_(2) reduction and cleaving the MnH–H–TEOA bond in the hydrogen evolution reaction. We explain the preference for CO_(2) conversion to CO over H_(2) evolution due to the higher energy barrier in forming the Mn-H_(2) species during H_(2) production. Our findings suggest the potential for tuning the electron density of the Mn center to enhance reactivity and selectivity in CO_(2) reduction. Additionally, we analyze potential competing reactions, focusing on electrocatalytic processes for CO_(2) reduction and evaluating “protonation-first” and “reduction-first” pathways through density functional theory calculations of redox potentials and Gibbs free energies. This analysis indicates the predominance of the “reduction-first” pathway in CO production, especially under high applied potential conditions. Moreover, our research highlights the selectivity of [Mn(pyrox)(CO)3Br] toward CO production over HCOO– and H_(2) formation, proposing avenues for future research to expand upon these findings by using larger basis sets and exploring additional functionalized ligands.
基金supported by the National Science Foundation Grant DMR-1904702the Defense Threat Reduction Agency Joint Science and Technology Office for ChemicalBiological Defense under grant number HDTRA1-18-1-0014.
文摘Inflammatory cytokines are key players in modulating immune responses to mount effective host defense.However,excessive production of inflammatory cytokines contributes to the destructive components responsible for various inflammatory disorders.As a result,treatment strategies have been developed to lower the cytokine levels or block their bioactivity.In particular,therapeutic agents that directly capture and neutralize cytokines have gained significant attention as they bypass the interactions with the host cells,and therefore,are less likely to induce immunogenic response and clearance.Among them,“monoplex”platforms such as cytokine-neutralizing antibodies(CNAs)are commonly designed to target a specific cytokine for neutralization.Meanwhile,to address the multiplexity of the cytokine targets in diseases,multiplex platforms such as glycosaminoglycan-containing biomaterials and cell-membrane-coated nanoparticles are emerging.Herein,we have reviewed the recent progress of these cytokine-neutralizing platforms(CNPs)and discussed their applications in treating inflammatory disorders.Overall,understanding the structure–function relationships underlying these CNPs would lead to the design of novel therapeutics toward effective management of inflammatory diseases.
基金supported by grants of the National Natural Science Foundation of China(Nos.5197116,81671829).
文摘With tremendous research advances in biomedical application,liquid metals(LM)also offer fantastic chemistry for synthesis of novel nano-composites.Herein,as a pioneering trial,litchi-shaped heterogeneous eutectic gallium indium-Au nanoparticles(EGaIn-Au NPs),served as effective radiosensitizer and photothermal agent for radio-photothermal cancer therapy,have been successfully prepared using in situ interfacial galvanic replacement reaction.The enhanced photothermal conversion efficiency and boosted radio-sensitization effect could be achieved with the reduction of Au nanodots onto the eutectic gallium indium(EGaIn)NPs surface.Most importantly,the growth of tumor could be effectively inhibited under the combined radio-photothermal therapy mediated by EGaIn-Au NPs.Inspired by this approach,in situ interfacial galvanic replacement reaction may open a novel strategy to fabricate LM-based nano-composite with advanced multi-functionalities.